Hybrid polymers for phase change ink jet inks and method of printing therewith

ABSTRACT

Phase change (hot melt) ink compositions for use in a phase change (hot melt) ink jet recording device in which recording is conducted by thermally melting the ink at a temperature above ambient temperature (20° C.) to provide prints that possess high quality images, scratch resistance, abrasion resistance, low-temperature storage stability and flexibility, offset and pick resistance, adhesion, and other desired properties are disclosed to comprise: 
     (a) from about 0.1% to about 30% of one or more colorants; and 
     (b) from about 0.1 to about 99.9% of one or more hybrid polymers. 
     Components other than those listed above may be included in the ink compositions to achieve specific printer, substrate, or end use requirements. Furthermore, the present invention also includes methods for the preparation of hybrid polymers and for their use in the above-described inks.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to ink jet inks for use in ink jet printers. Moreparticularly, this invention relates to phase change, or hot melt, inkjet inks for use in ink jet printers from which ink is propelled fromthe printer nozzle by heat or by a pressure wave.

2. Description of Related Art (Including Information Disclosed Under 37CFR 1.97 and 37 CFR 1.98)

Ink jet printing involves the placement in response to a digital signalof small drops of a fluid ink onto a surface to form an image withoutphysical contact between the printing device and the surface. The methodof drop generation varies among the different ink jet technologies andcan be used to classify ink jet printing into two major technologytypes, continuous (CIJ) and drop-on-demand (DOD).

In CIJ printing systems, a continuous stream of liquid ink droplets isejected from a nozzle and is directed, with the assistance of anelectrostatic charging device in close proximity to the print head,either to a substrate to form a printed image or to a recirculatingsystem. Inks for CIJ printing systems are typically based on solventssuch as methyl ethyl ketone and ethanol.

In DOD ink jet printing systems, liquid ink droplets are propelled froma nozzle by heat (thermal or bubble ink jet) or by a pressure wave(piezo ink jet). Unlike CIJ systems, all the ink droplets are used toform the printed image and are ejected when needed, "on demand." Nodeflection of ink droplets is involved. Thermal or bubble ink jet inkstypically are based on water and glycols. Piezo ink jet systemsgenerally use aqueous, solvent, or solid inks. These last inks, alsoknown as phase change inks, are solid at ambient temperature and liquidat printing temperatures. It is these inks to which the presentinvention relates.

The following properties are required of an ink composition for ink jetprinting:

(a) high quality printing (edge acuity and optical density) of text andgraphics on substrates, in particular, on uncoated cellulosic paper,

(b) short dry time of the ink on a substrate and good adhesion such thatafter printing the print is not smudged when rubbed or offset onto asubsequent printed image placed upon the print,

(c) good jetting properties exhibited by a lack of deviation of inkdroplets from the flight path (misplaced dots) and of ink starvationduring conditions of high ink demand (missing dots),

(d) resistance of the ink after drying on a substrate to water and tosolvents,

(e) long-term storage stability (no pigment settling) and

(f) long-term reliability (no corrosion or nozzle clogging).

Inks are known that possess one or more of the above listed properties.However, few inks are known that possess all of the above listedproperties. Often, the inclusion of an ink component meant to satisfyone of the above requirements can prevent another requirement from beingmet. For example, the inclusion of a polymer in the ink composition canimprove the adhesion of the ink to the substrate. However, the polymercan impair the jetting of the ink because of the behavior of the polymerunder the high shear conditions of jetting (10⁴ -10⁶ sec⁻¹). Thus, mostcommercial ink jet inks represent a compromise in an attempt to achieveat least an adequate response in meeting all of the above listedrequirements.

The use of polymers in phase change (hot melt) inks and the printing ofsuch inks has been disclosed in the following publications:

U.S. Pat. No. 5,006,170 teaches the use of "rosin esters" with acolorant and a propellant.

U.S. Pat. No. 5,531,819 teaches the use of an "acrylic resin," "rosinresin," "hydrogenated rosin resin," "petroleum resin," "hydrogenatedpetroleum resin," "or "terpene resin" with a wax, a colorant, and aplasticizer.

U.S. Pat. No. 5,354,368 discloses the use of a "tall oil rosin having ahigh acid number" with a rheology modifier. Given as examples of "talloil rosin" are "natural tall oil and wood rosins as well as modifiedtall oil and wood rosins and tall oil and wood rosin derivatives."

U.S. Pat. No. 5,397,388 teaches the use of "acrylic resin," "rosinresin," "petroleum resin," "modified petroleum resin," "hydrogenatedpetroleum resin," or "terpene resin," with a wax, an organic substancemiscible with the wax, and a colorant.

U.S. Pat. No. 5,409,530 teaches the use of a resin selected from thegroup consisting of "rosins, rosin derivatives, terpenes, [or] modifiedterpenes . . . " with a second component to dissolve the resin.

U.S. Pat. No. 5,514,209 discloses the use of a "glycerol ester of ahydrogenated rosin" with a microcrystalline wax.

U.S. Pat. No. 5,620,508 teaches the use of "rosin-type resins" withpigments and oil-soluble dyes. Given as examples of rosin-type resinsare "rosins, hydrogenated rosins, disproportionated rosins, rosinesters, rosin-modified phenolic resins, rosin-modified maleic acidresins, and rosin-modified xylene resins."

Also, EP 0 739 958 A2 teaches the use of an "acrylic resin," "rosinresin," "petroleum resin," "modified petroleum resin," "hydrogenatedpetroleum resin," or "terpene resin," with at least one wax, a colorant,and a second resin. One resin has a softening point from roomtemperature to 100° C., and the other resin has a softening point from50° C. to 1 50° C.

While the prior art teaches the use of many classes of polymers in phasechange (hot melt) inks, the ability of using different classes ofpolymers within the same ink composition can be limited due tocompatibility of the polymers with each other. Furthermore, printedimages made with inks that contain certain polymers that have poorquality images and lack scratch resistance, low-temperature storagestability and flexibility, offset and pick resistance, adhesion, andother desired properties.

The essential component of the present invention is a hybid polymer.This polymer is prepared by chemically attaching one class of polymer toanother. For example, a useful polymer is one that has an acrylicpolymer attached to a rosin polymer. The novel aspect of using a hybridpolymer in a phase change (hot melt) ink is that it allows two polymersthat are incompatible when added individually in the ink composition tobe rendered compatible in the ink composition when used in the state inwhich the polymers are chemically joined together. This allows theunique property enhancing attributes of two incompatible polymers to beexploited in the same ink composition. Such hybrid polymers suitable forphase change (hot melt) inks are unknown. Hybrid polymers can be used asthe sole polymer of the ink composition, in combination with otherhybrid polymers, or in combination with other polymers.

In accordance with the present invention, the preparation of phasechange (hot melt) inks useful in ink jet printing devices is provided.The phase change (hot melt) inks preferably are for use in a piezo inkjet printer with which recording is conducted by thermally melting anink composition at a temperature above ambient temperature (20° C.) andthen ejecting the ink composition onto a porous or non-porous substratesuch as paper, aluminum, glass, metal, wood, synthetic polymer films,and textiles. Furthermore, the present invention also provides methodsfor the preparation of hybrid polymers and for their use in theabove-described inks.

The present invention overcomes many of the problems associated with theuse of prior art phase change (hot melt) ink compositions whileachieving distinct advantages thereof. Accordingly, an object of thepresent invention is to provide improved ink compositions capable ofsatisfying simultaneously the properties required of an ink compositionfor ink jet printing, especially the aforementioned properties (a) to(f) and which comprise a hybrid polymer. Other objects and advantages ofthe present invention will become apparent from the followingdisclosure.

SUMMARY OF THE INVENTION

In accordance with the present invention, the preparation of phasechange (hot melt) inks useful in ink jet, hot melt gravure, and similarprinting devices is provided. The phase change (hot melt) inkspreferably are for use in a phase change (hot melt) ink jet recordingdevice in which recording is conducted by thermally melting the ink at atemperature above ambient temperature (20° C.) to provide prints thatpossess high quality images, scratch resistance, abrasion resistance,low-temperature storage stability and flexibility, offset and pickresistance, adhesion, and other desired properties. Furthermore, thepresent invention also includes methods for the preparation of hybridpolymers and for their use in the above-described inks.

In accordance with the present invention, the ink compositions comprise:

(a) from about 0.1% to about 30% of one or more colorants; and

(b) from about 0.1 to about 99.9% of one or more hybrid polymers.

Components other than those listed above may be included in the inkcompositions to achieve specific printer, substrate, or end userequirements.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

The phase change (hot melt) inks of the present invention comprise acolorant and a hybrid polymer. Other components that may be added,include but are not limited to, waxes, polymers, antioxidants, biocides,and corrosion inhibitors.

Colorants

Coloring agents that may be incorporated in the ink composition includepigments and dyes. Any dye or pigment or combination of one or more dyesor pigments may be used as long as the colorant can be dispersed in theink composition and is compatible with the other components of thecomposition. The coloring material of the present invention ispreferably a pigment.

No particular limitation is imposed on the type or the amount of pigmentused. The term "pigment" refers to a solvent insoluble colorant. A largerange of pigments, organic and inorganic, may be used either alone or incombination. Pigments used in ink jet inks typically are in thedispersed state and are kept from agglomerating and settling out of thecarrier medium by placing acidic or basic functional groups on thesurface of the pigments, attaching a polymer onto the surface of thepigments, or adding a surfactant to the ink.

The amount of the pigment present in the ink compositions is from about0.1 to 30 wt %, preferably from about 2 to 10 wt %. Examples of apigment that may be used in the practice of the present invention for ayellow ink include C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, andC.I. Pigment Yellow 13. Examples of a pigment that may be used in thepresent invention for a magenta ink include C.I. Pigment Red 5, C.I.Pigment Red 7, C.I. Pigment Red 12, C.I. Pigment Red 112, and C.I.Pigment Red 122. Examples of a pigment that may be used in the presentinvention for a cyan ink include C.I. Pigment Blue 1, C.I. Pigment Blue2, C.I. Pigment Blue 16, C.I. Vat Blue 4, and C.I. Vat Blue 6.

The pigment particles need to be small enough in size so that they movefreely through the printing device. Because the ejecting nozzles of inkjet ink printers range in diameter from about 10 to 100 microns,pigments suitable for use in the present invention may have a range ofparticle sizes from about 0.01 microns to 100 microns, preferably fromabout 0.01 microns to 10 microns, and more preferably from about 0.01microns to 5 microns.

No particular limitation is imposed on the type or the amount of dyeused. Dyes which are useful in the present invention are those which arewater soluble or water-insoluble such as basic, acid, and direct dyes.If desired, the dyes can be reactive dyes which contain groups capableof forming covalent bonds with textile materials. The amount of dyepresent in the ink compositions is from about 0.1 to 30 wt %, preferablyfrom about 2 to 10 wt %.

Fine particles of metal or metal oxides also may be included ascolorants for the compositions of the present invention. Metal and metaloxides are used in the preparation of magnetic ink jet inks. Examplesmay include silica, alumina, titania, and finely divided copper.

Hybrid Polymers

The essential component of the present invention is a hybrid polymer.This polymer is prepared by chemically attaching one class of polymer toanother. The novel aspect of using a hybrid polymer in a phase change(hot melt) ink is that it allows two polymers that are incompatible inthe ink formulation to be rendered compatible in the ink formulationwhen used in the state in which the polymers are chemically joined toeach other. This allows the unique property enhancing attributes of twoincompatible polymers to be exploited in the same ink composition.Hybrid polymers can be used as the sole polymer of the ink formulationor in combination with other polymers, including other hybrid polymers.

The polymers suitable for use in the present inventions may includenaturally occurring polymers such as alginic acid, carboxymethylcellulose, and pectinic acid; synthetic analogues of naturally occurringpolymers such as rosin esters, lignosulfanates, nitrocellulose, andalcohol-soluble polysaccharides; synthetic polymers such aspolyacrylamide, polyacrylic acid, polyethylene oxide, polyethyleneglycol, polymethacrylic acid, polyitaconic acid, polymaleic acid,polyvinyl alcohol, and polyvinyl methyl ether; and synthetic copolymerssuch as styrene/acrylic acid, ethylene/vinyl acetate, acrylicacid/N-vinyl pyrrolidinone, and vinylnaphthalene/itaconate copolymers.The copolymers may be block, graft, tapered, branched, and randomcopolymers. Methods of polymerization include solution, emulsion,suspension, and bulk polymerization. While physical properties of thepolymers can be affected by the polymerization method, the resultantpolymers can provide the desired outcomes of the invention.

No particular limitation is imposed on the physical properties of thepolymers. Preferred polymers are those having an acid number in therange of from about 10 to 300, a weight average molecular weight in therange of from about 500 to 250,000, a softening point in the range offrom about 0 to 150° C., and a glass transition temperature of in therange of from about -25 to 1 80° C. More preferred polymers are thosehaving an acid number in the range of from about 20 to 80, a weightaverage molecular weight in the range of from about 2000 to 35,000, asoftening point in the range of from about 40 to 90° C., and a glasstransition temperature from about 25 to 80° C.

Waxes

Any one of known waxes may be used in the phase change (hot melt) inkformulation with no particular restriction. A preferred wax is solid atroom temperature and is molten sufficiently at the operating temperatureof the printing device. Examples of suitable waxes include petroleumwaxes, such as paraffin wax and micro crystalline wax; plant waxes, suchcandelilla wax and carnauba wax; animal waxes, such as bees wax andlanolin; synthetic hydrocarbon waxes, such as a Fisher-Tropsch wax and apolyethylene wax; higher fatty acids, such as stearic acid and lauricacid; higher alcohols, such as stearyl alcohol and 12-hydroxystearicacid; and derivatives thereof and combinations thereof. These waxes maybe used alone in the ink formulation or admixed with one or more otherwaxes.

Polymers

Polymers used in phase change (hot melt) inks of the present inventiongenerally have melting points in the range of about 40° C. to 200° C.,and preferably from about 60° C.to 140° C. The polymer should bethermally stable in a molten state so that gaseous products are notgenerated or deposits on the printer device are not formed.

Examples of suitable polymers for ink compositions of the presentinvention include, but are not limited to, one or more of the following:alkyd resins; amides; acrylic polymers; benzoate esters; citrateplasticizers; cumarone-indene resins; dimer fatty acids; epoxy resins;fatty acids; ketone resins; maleate plasticizers; long chain alcohols;olefin resins; petroleum resins; phenolic resins; phthalateplasticizers; polyesters; polyvinyl alcohol resins; rosins; styreneresins; sulfones; sulfonamides; terpene resins; urethanes; vinyl resins;and derivatives thereof and combinations thereof. No limitation isplaced on the type or the amount of the polymer that is present in theink.

Antioxidants

Phase change (hot melt) ink compositions prepared in accordance with thepresent invention are in a molten state during printing. To preventthermally induced oxidation from occurring in this state, antioxidantsmay be added to the ink composition. Suitable antioxidants, presentpreferably in the amount of about 0.1% to 1.0% by weight of the inkcomposition, include, for example, Irganox® 1010 and Iragofos® 168(Ciba-Geigy Corp.).

Biocides

To prevent the growth of microorganisms, a biocide may be added,preferably in the range of about 0.01% to 5%, based on the weight of theink composition. Examples of suitable biocides include sorbic acid,vinylenebis-thiocyanate, bis(trichloromethyl)sulfone, and zincpyridinethione.

Corrosion Inhibitors

One or more corrosion inhibitors may be added to inhibit the corrosionof the metal that comes in contact with the phase change (hot melt) ink.Suitable corrosion inhibitors, present preferably in the range of about0.1% to 5% (based on the weight of the ink composition), includeammonium dinonyl naphthalene sulphonate.

Methods of Ink Preparation and Desired Ink Properties

No limitation is placed on the way in which the components of the phasechange (hot melt) ink compositions of the present invention are combinedin the preparation of the compositions. A preferred method involvesadding all the components, except the colorant and the hybrid polymer,heating the components at about 135° C., while slowly stirring, until ahomogenous mixture is obtained. Then, under the same conditions, thehybrid polymer is added at a rate such that a homogenous mixture isobtained. In this manner, more of the hybrid polymer can be incorporatedinto the ink composition. The coloring agent (pigment) is subsequentlyadded and stirring and heating are continued until the colorant isproperly dispersed. If a greater degree of dispersion is desired, adispersing machine such as a three roll mill, an attritor, a ball mill,or a colloid mill can be used. The molten mixture is then filtered toremove particles of a size too large for effective printing.

Inks suitable for use with phase change (hot melt) ink jet printersshould be solid at room temperature, by which is meant about 18° C. toabout 27° C., and are transformed into a molten state at temperaturesranging from 45° C. to 150° C. Most preferably these inks should meltfrom about 65° C. to 130° C. The phase change inks also should exhibit arelatively low melt viscosity of 1 to 50 cP between 100° C. and 150° C.,most preferably 5 to 20 cP. The inks also should exhibit excellentdispersion and stability of this dispersion, especially when exposed tothe elevated temperatures at which the ink is commonly stored and jettedin the printing device. The ink compositions of the present inventionmeet the aforementioned requirements.

Inks suitable for use with hot melt (phase change) ink jet printersshould provide prints with excellent quality (good edge acuity and highoptical density), and there should be no missing or misplaced dots. Theinks should dry quickly onto the printed substrate as well as adherewell to said substrate to provide a print with resistance to abrasion,water, and solvents. The ink compositions of the present invention meetthese requirements.

The ink compositions of the present invention possess desirablenon-Newtonian properties. That is, these inks exhibit a relatively highviscosity at relatively low shear rates, e.g., 12 cP or more, but a muchreduced viscosity at relatively high shear rates, e.g., 10⁴ sec⁻¹ ormore. The high viscosity at low shear helps to keep the colorant insuspension when the ink is being stored whereas the low viscosity athigh shear reduces the energy required to eject the ink droplet from theprinthead.

Methods of Printing

The compositions of the present invention may be used in phase change(hot melt) ink jet, hot melt gravure, and similar printing methods. Apreferred method of printing involves phase change (hot melt) ink jetprinting using piezo ink jet printers. The specific ink jet printeremployed is not critical.

Substrates

No limitation is placed on the substrate that can be used in thepractice of the present invention. The compositions of this inventioncan be applied to a wide range of porous and non-porous substrates suchas paper, aluminum, glass, metal, wood, synthetic polymer films, andtextiles. The temperature of the substrate can be adjusted to improveproperties such as print quality and adhesion. For example, thesubstrate can be passed through heated rollers subsequent to printing toimprove print quality by increasing dot gain. Also, the temperature ofthe ink ejected from the printer can be raised so that when it comesinto contact with a compliant substrate, such as plastic, enhancedadhesion can occur due to partial fusing.

Specific embodiments of the phase change (hot melt) inks of the presentinvention are provided in further detail herein below. These examplesare intended to be illustrative, and the invention is not limited to thematerials set forth in these embodiments. All parts are by weight unlessotherwise noted.

EXAMPLE 1 Preparation of Hydrocarbon Polymer 7173-69

To a one-gallon Parr reactor were charged 2100 parts ofdicyclopentadiene (DCPD) and 900 parts of LRO-90, both products ofLyondell Chemical Corporation. The contents were heated to 105° C. overa 30-minute period while sparging with nitrogen. Then, the nitrogen wasturned off, the reactor was sealed, and the temperature was increased to275° C. over a 2.5-hour period and was maintained at that temperaturefor a five-hour period. The temperature of the polymer was allowed tocool to 180° C. over a 30-minute period and then the polymer wasdischarged.

EXAMPLE 2 Preparation of Hydrocarbon/Acrylic Hybrid Polymer 7521-11

To a one-gallon Parr reactor was added 1065 parts of dicyclopentadiene(DCPD), 450 parts of LRO-90, 55 parts of Neodene 16 (Shell Oil Company),and 350 parts of acrylic polymer JONREZ® H-2704 (manufactured andmarketed by Westvaco Corporation). The contents were heated to atemperature of 105° C. and held for a period of 30 minutes at thattemperature while sparging with nitrogen. The nitrogen was turned off,the reactor was sealed, and the contents were heated to a temperature of260° C. The temperature was maintained at 260° C. for a period of fivehours and then was allowed to cool to a temperature of 190° C. Thecontents were brought to atmospheric pressure and were discharged into athree-liter, five-neck, round-bottom flask equipped with an overheadstirrer, a thermocouple, a nitrogen sparge tube, a stopper, and aDean-Stark trap and condenser. The contents of the flask were heated toa temperature of 260° C. while sparging with nitrogen. The nitrogensparge was continued at 260° C. for approximately four hours until nofurther distillate was collected in the Dean-Stark trap. The resultingpolymer had an acid number of 2.8, a ring and ball softening point of131° C., a DSC glass transition temperature of 75° C., a weight averagemolecular weight of 6600, a polydispersity of 4.1, a Gardner color valueof 12, and a Brookfield viscosity at 150° C. of greater than 10,000 cP(#18 spindle).

EXAMPLE 3 Preparation of Phase Change Ink 7521-36

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 60.1 parts of Versamid® 754 (a dimer acid-based polyamide resinproduct of Henkel), 35.4 parts of paraffin wax, and 52.3 parts ofHallcomide® M-18-OL (N,N-dimethyl oleoamide, a product of The C. P. HallCo.). The contents were heated to a temperature of 135° C. under anitrogen atmosphere. Then, 7.0 parts of hydrocarbon polymer 7173-69 wereadded over a one-hour period. The contents were maintained at atemperature of 135° C. for an additional hour.

EXAMPLE 4 Preparation of Phase Change Ink 7521-37

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 35.4 parts of paraffin wax, 52.3 parts of Hallcomid® M-18-OL, and60.1 parts of Versamid® 754. The contents were heated to a temperatureof 135° C. under a nitrogen atmosphere. Then, 5.0 parts of acrylicpolymer JONREZ® H-2704 were added over a one-hour period. The contentswere maintained at a temperature of 135° C. for an additional hour.

EXAMPLE 5 Preparation of Phase Change Ink 7521-38

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 35.4 parts of paraffin wax, 52.3 parts of Hallcomid® M-18-OL, and60.1 parts of Versamid® 754. The contents were heated to a temperatureof 135° C. under a nitrogen atmosphere. Then, 4.0 parts of hybridpolymer 7521-11 and 1.0 parts of JONREZ® H-2704 were added over aone-hour period. The contents were maintained at a temperature of 135°C. for an additional hour.

EXAMPLE 6 Preparation of Phase Change Ink 7536-06

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 35.4 parts of paraffin wax, 52.3 parts of Hallcomid® M-18-OL, and60.1 parts of Versamid® 754. The contents were heated to a temperatureof 135° C. under a nitrogen atmosphere. Then, 42 parts ofhydrocarbon/acrylic hybrid polymer 7521-11 were added over a two-hourperiod and stirred for 1 hour at 135° C. The contents were maintained ata temperature of 135° C. for an additional hour.

EXAMPLE 7

Hydrocarbon polymers provide phase change (hot melt) inks withflexibility and acrylic polymers provide adhesion and abrasionresistance. However, in some ink systems, the incorporation of bothpolymers at a level that permits the benefit of both polymers to beachieved cannot be accomplished due to incompatibility of the polymers.As an example, a composition consisting of 35.4 grams of paraffin, 52.3grams of Hallcomid® M-18-OL, and 60.1 grams of Versamid® 754, wasprepared. When 7.0 grams or more of hydrocarbon polymer 7173-69(Example 1) was added to the composition, an incompatible ink system wasobtained (Example 3). Likewise, adding 5.0 grams or more of acrylicpolymer JONREZ® H-2704 to the same composition also results in anincompatible ink system (Example 4).

By chemically attaching together 82 wt % of hydrocarbon monomers and 18wt % of acrylic polymer JONREZ® H-2704, however, hydrocarbon/acrylichybrid polymer 7521-11 was obtained (Example 2). This hybrid polymer wasadded at a level of 42.3 parts to the previously described compositionwithout an incompatible system resulting (Example 6). Adding the hybridpolymer to the composition is equivalent to adding 7.6 grams of acrylicpolymer JONREZ® H-2704 and 34.7 grams of hydrocarbon polymer 7136-69.

To demonstrate the uniqueness of the hybrid approach in achieving acompatible ink system, a blend of 4.0 parts of hydrocarbon polymer7136-69 (Example 1) and 1.0 part of acrylic polymer JONREZ® H-2704 wasadded to the same composition (Example 5). In this case, an incompatibleink system was obtained. Thus, a much greater amount of an acrylicpolymer and a hydrocarbon polymer can be added to a wax/fatty acid-basedphase change ink-jet ink formulation in the hybrid form than as a blend.The comparisons described in Examples 1-7 are summarized in Table I.

                  TABLE I                                                         ______________________________________                                        Phase Change Ink-Jet Ink Formulas                                                             Ink      Ink     Ink   Ink                                      7521-36 7521-37 7521-38 7536-06                                             ______________________________________                                        Paraffin, parts 35.4     35.4    35.4  35.4                                     Hallcomid ® M-18-OL, parts 52.3 52.3 52.3 52.3                            Versamid ® 754, parts 60.1 60.1 60.1 60.1                                 Polymer 7173-69, parts 7.0  4.0                                               JONREZ ® H-2704, parts  5.0 1.0                                           Hybrid Polymer 7521-11, parts    42.3                                         Compatible no no no yes                                                     ______________________________________                                    

EXAMPLE 8 Preparation of Rosin Polymer 7485-70

To a three-liter, five-neck, round-bottom flask equipped with anoverhead stirrer, a thermocouple, a condenser, and two stoppers wereadded 1000 parts of Westvaco Corporation's Rosin SS and 49 parts ofWestvaco Corporation's L5 fatty acid. The contents of the flask wereheated to a temperature of 185° C. At a temperature of 185° C., 60 partsof maleic anhydride (from Aldrich Chemical Company) were added. Thetemperature was increased to 205° C. and was maintained for one hour.Then, 144 parts of glycerol (Aldrich) and 1.3 parts of magnesium oxide(Aldrich) were added. A Dean-Stark trap was attached to the flask andthe contents of the flask were heated to a temperature of 275° C. over aone-hour period. The temperature was held at 275° C. for a period of twohours. The resulting polymer had an acid number of 22, a ring and ballsoftening point of 86° C., a DSC glass transition temperature of 39° C.,a weight average molecular weight of 1500, a polydispersity of 1.5, aneat Gardner color value of 11, and a Brookfield viscosity at 135° C. of2200 cP (#18 spindle).

EXAMPLE 9 Preparation of Rosin/Acrylic Hybrid Polymer 7490-97

To a three-liter, five-neck, round-bottom flask equipped with anoverhead stirrer, a thermocouple, a condenser, and two stoppers wereadded 950 parts of Rosin SS and 225 parts of LIA Special fatty acid. Thecontents were heated to a temperature of 185° C. Then, 40 parts ofmaleic anhydride were added. The temperature was increased to 205° C.and was maintained for a period of one hour. Then, 10 parts of glycerol,20 parts of pentaerythritol (Aldrich), and 2 parts of magnesium oxidewere charged. A Dean-Stark trap was attached and the contents wereheated to a temperature of 275° C. over a one-hour period. Then, 325parts of acrylic polymer JONREZ® H-2704 were added. The reactiontemperature was maintained for an additional two hours at 275° C. Theresulting polymer had an acid number of 11, a ring and ball softeningpoint of 59° C., a DSC glass transition temperature of 5° C., a weightaverage molecular weight of 5300, a polydispersity of 30, a neat Gardnercolor value of 9.5, and a Brookfield viscosity at 145° C. of 500 cP (#18spindle).

EXAMPLE 10 Preparation of Phase Change Ink 7513-88

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 20.0 parts of carnauba wax, 105.6 parts of paraffin wax, 22.2parts of Elvax, and 72.2 parts of L1A Special fatty acid (Westvaco). Thecontents were heated to 135° C. under a nitrogen atmosphere. Then, 190.0parts of rosin polymer 7485-70 were charged over a two-hour period. Thecontents were maintained at a temperature of 35° C. for an additionalhour.

EXAMPLE 11 Preparation of Phase Change Ink 7513-89

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 20.0 parts of carauba wax, 105.6 parts of paraffin wax (FlukaChemika), 22.2 parts of Elvax® 40W (ethylene vinyl acetate resin fromE.I. DuPont de Nemours & Co., Inc.), and 72.2 parts of L1A Special fattyacid. The contents were heated to 35° C. under a nitrogen atmosphere.Then, 5.9 parts of JONREZ® H-2704 were charged over a two-hour period.The contents were maintained at a temperature of 135° C. for anadditional hour.

EXAMPLE 12 Preparation of Phase Change Ink 7513-91

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 20.0 parts of carnauba wax (Aldrich), 105.6 parts of paraffin wax,22.2 parts of Elvax® 40 W, and 72.2 parts of L1A Special fatty acid. Thecontents were heated to 135° C. under a nitrogen atmosphere. Then, 5.4parts of rosin polymer 7485-70 and 1.4 parts of acrylic polymer JONREZ®H-2704 were charged over a two-hour period. The contents were maintainedat a temperature of 135° C. for an additional hour.

EXAMPLE 13 Preparation of Phase Change Ink 7513-74

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a therrnocouple, and a stopper wereadded 20.0 parts of camauba wax, 105.6 parts of paraffin wax, 22.2 partsof Elvax® 40W, and 72.2 parts of L1A Special fatty acid. The contentswere heated to 135° C. under a nitrogen atmosphere. Then, 132.0 parts ofrosin/acrylic hybrid polymer 7490-97 were charged over a two-hourperiod. The contents were maintained at a temperature of 135° C. for anadditional hour.

EXAMPLE 14

Rosin polymers provide phase change (hot melt) inks with flexibility andadhesion. In addition, the polymers can improve the dispersion of thecolorant. Like hydrocarbon polymers, in some ink systems, rosin polymerscannot be used with acrylic polymers at a level that permits the benefitof both polymers to be achieved due to incompatibility of the polymers.As an example, a composition consisting of 105.6 parts of paraffin, 72.2parts of Westvaco L1A Special fatty acid, 22.2 parts of Elvax® 40W, and20.0 parts of carnauba wax was prepared. When 190.0 grams or more ofrosin polymer 7485-70 was added to the composition, a compatible systemresulted (Example 10). When 5.9 parts or more of acrylic polymer JONREZ®H-2704 were added to the same composition, an incompatible ink systemwas obtained (Example 11). By chemically attaching together 80 wt % ofrosin polymer 7485-70 and 20 wt % of acrylic polymer JONREZ® H-2704,rosin/acrylic hybrid polymer 7490-97 was obtained (Example 9). Thishybrid polymer was added at a level of 132.0 parts to the previouscomposition without an incompatible system resulting (Example 13).Adding the hybrid polymer to the composition is equivalent to adding26.4 parts of acrylic polymer JONREZ® H-2704 and 105.6 parts of rosinpolymer 7485-70.

To demonstrate the uniqueness of the hybrid approach in achieving acompatible system, a blend of 5.4 parts of rosin polymer 7485-70 and 1.4parts of acrylic polymer JONREZ® H-2704 was added to the previouscomposition (Example 12). An incompatible ink system was obtained. Thus,a greater amount of an acrylic polymer can be incorporated in awax/fatty acid/ethylene vinyl acetate-based phase change ink in thehybrid form than as a blend. The comparisons described in Examples 10-14are summarized in Table II.

                  TABLE II                                                        ______________________________________                                        Phase Change Ink-Jet Ink Formulas                                                             Ink      Ink     Ink   Ink                                      7513-88 7513-89 7513-91 7513-74                                             ______________________________________                                        Paraffin, parts 105.6    105.6   105.6 105.6                                    Carnauba wax, parts 20.0 20.0 20.0 20.0                                       Elvax ®, parts 22.2 22.2 22.2 22.2                                        Westvaco L1A fatty acid, parts 72.2 72.2 72.2 72.2                            Rosin polymer 7485-70, parts 190.0  5.4                                       JONREZ ® H-2704, parts  5.9 1.4                                           Hybrid Resin 7490-97, parts    132.0                                          Compatible yes no no yes                                                    ______________________________________                                    

EXAMPLE 15 Preparation of Rosin/Polyurethane Hybrid Polymer 7485-57

To a three-liter, five-neck, round-bottom flask equipped with anoverhead stirrer, a thermocouple, a condenser, and two stoppers wereadded 1,000 parts of Westvaco Rosin SS and 65.4 parts of L5 fatty acid.The contents were heated to a temperature of 185° C. Then, 65.4 parts ofmaleic anhydride were added. The temperature was increased to 205° C.and maintained for a period of one hour. Then, 131 parts ofpentaerythritol and 4.4 parts of magnesium oxide were charged. ADean-Stark trap was attached, and the contents were heated to atemperature of 270° C. over a one-hour period. The temperature wasmaintained at 270° C. for a period of one hour. Then 201 parts ofpolyurethane K-Flex® UD 320-100 were added. The temperature wasmaintained for an additional two hours at 270° C. The resulting polymerhad an acid number of 8, a ring and ball softening point of 90° C., aDSC glass transition temperature of 44° C., a weight average molecularweight of 2,200, a polydispersity of 1.8, a neat Gardner color value of17, and a Brookfield viscosity of 135 cP (#8 spindle).

EXAMPLE 16 Preparation of Phase Change Ink 7513-48D

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 20.0 parts of carnauba wax, 105.6 parts of paraffin wax, 22.2parts of Elvax® 40W, and 72.2 parts of L1A Special fatty acid. Thecontents were heated to 135° C. under a nitrogen atmosphere. Then, 3.0parts of K-Flex® PU UD-320-100 were charged.

EXAMPLE 17 Preparation of Phase Change Ink 7504-48A

To a 500-mL, five-neck, round-bottom flask equipped with an overheadstirrer, a nitrogen delivery tube, a thermocouple, and a stopper wereadded 20 parts of carnauba wax, 105.6 parts of paraffin wax, 22.2 partsof Elvax® 40W, and 72.2 parts of L1A Special fatty acid. The contentswere heated to 135° C. under a nitrogen atmosphere. Then, 310.0 parts ofrosin/polyurethane hybrid polymer 7485-57 were charged over a two-hourperiod. The contents were maintained at a temperature of 135° C. for anadditional hour.

EXAMPLE 18

Polyurethane polymers provide phase change (hot melt) inks withexcellent abrasion and chemical resistance. Rosin polymers provide phasechange (hot melt) inks with flexibility and adhesion. In addition, rosinpolymers can improve the dispersion of the colorant. In some inkformulations, polyurethane and rosin polymers, because ofincompatibility of the polymers, cannot be used together at a level thatallows the benefit of both polymers to be achieved. For example, a phasechange ink composition consisting of 105.6 parts of paraffin, 72.2 partsof Westvaco L1A Special fatty acid, 22.2 parts of Elvax® 40W, and 20.0parts of carnauba wax was prepared. When 190.0 parts or more of rosinpolymer 7485-70 were added to the composition, a compatible ink systemresulted (Example 11). Adding 3.0 parts or more of polyurethane polymerK-Flex®" PU UD-320-100 to the same composition resulted in anincompatible system (Example 16). By chemically attaching together 65 wt% of rosin polymer 7485-70 and 35 wt % of polyurethane polymer K-Flex®PU UD-320-100, rosin/polyurethane hybrid polymer 7485-57 was obtained(Example 15). This hybrid polymer was added at a level of 310.0 parts tothe same ink composition without an incompatible system resulting(Example 17). Adding the hybrid polymer is equivalent to adding 108.5parts of urethane polymer K-Flex® PU UD-320-1 00 and 201.5 parts ofrosin polymer 7485-70. Thus, a much greater amount of a polyurethanepolymer can be added to a wax/fatty acid/ethylene vinyl acetate-basedphase change ink formulation in the hybrid form than alone. Thecomparisons described in Examples 16-18 are summarized in Table III.

                  TABLE III                                                       ______________________________________                                        Phase Change Ink-Jet Ink Formulas                                                            Ink    Ink       Ink                                             7513-88 7504-48D 7504-48A                                                   ______________________________________                                        Parafin wax, parts                                                                             105.6    105.6     105.6                                       Carnauba wax, parts 20.0 20.0 20.0                                            Elvax, parts 22.2 22.2 22.2                                                   Westvaco L1A fatty acid, parts 72.2 72.2 72.2                                 Rosin Polymer 7485-70, parts 190.0                                            K-Flex ® PU UD-320-100, parts  3.0                                        Hybrid Polymer 7485-57, parts   310.0                                         Compatible yes no yes                                                       ______________________________________                                    

EXAMPLE 19

The properties of several compositions prepared in previous exampleswere determined:

Flexibility of Printed Ink. A small aluminum dish was coated with a thinfilm of the hot melt ink, and the dish was stored at -4° C. for 15minutes. The pan was then flexed back and forth at -4° C. to determinethe flexibility of the different hot melt inks.

Offset Temperature (Block Resistance) of Printed Ink. A piece ofuncoated, standard Nashua office paper was printed with a 1 milthickness of the ink under examination. A second piece of uncoated paperwas placed on top of the printed piece, and a pressure of 500 g/in² wasapplied for two minutes. This procedure was repeated at increasingtemperature intervals of 5° C. for two minutes to determine thetemperature where print transfer from the print to the uncoated paperoccurred (the offset temperature).

Abrasion Resistance of Printed Ink. A piece of standard Nashua officepaper coated with a 1 mil thickness of a hot melt ink was moved back andforth approximately 20 times over a similarly coated print using aSutherland abrasion resistance tester equipped with a 2 lb. weight. Thenumber and size of the resulting grooves and scratches in the printswere then evaluated.

Determination of Adhesion of Printed Ink. A steel bar containing a pieceof scotch tape was placed in contact with another bar which had a pieceof Nashua paper coated with a hot melt ink of 1 mil thickness fixed toit. The steel bars were pulled apart at a constant rate using a MonsantoTel-Tak tack tester, and the print as well as the scotch tape wereexamined to determine the adhesion of the ink to the paper.

The results of the evaluation of the properties of the above-identifiedcompositions are given in Table IV. The best flexibility, abrasionresistance, and adhesion were obtained with composition 7513-74.

                  TABLE IV                                                        ______________________________________                                        Properties of Phase Change (Hot Melt) Inks                                    ______________________________________                                        Ink       7536-06    7513-74   7504-48A                                                                              7536-09                                  Hybrid Polymer 7521-11 7490-97 7485-57 7585-70                                 Hydrocarbon/ Rosin/acrylic Rosin/ Rosin                                       acrylic  polyurethane                                                        Viscosity, cP 75 55 135 50                                                    Flexibility 8 9 7 9                                                           Offset Temp.,  55 60 60 45                                                    ° C.                                                                   Abrasion 6 7 4 5                                                              Resistance                                                                    Adhesion 7 9 8 8                                                            ______________________________________                                    

From this disclosure it should be understood that the subject matter ofthis invention is:

(1) An ink jet ink composition comprising a colorant and a hybridpolymer;

(2) the ink jet ink composition of (1) wherein the composition is aphase change ink jet ink;

(3) the ink jet ink composition of (2) wherein the colorant is a memberof the group of colorants selected from pigments, dyes, metals, metaloxides, and combinations thereof;

(4) The ink jet ink composition of (3) wherein the pigment is selectedfrom the group of organic and inorganic water-insoluble colorants andcombinations thereof;

(5) the ink jet ink composition of (4) wherein the pigment is selectedfrom the group of pigments consisting of C.I. Pigment Yellow 1, C.I.Pigment Yellow 3, C.I. Pigment Yellow 13, C.I. Pigment Red 5, C.I.Pigment Red 7, C.I. Pigment Red 12, C.I. Pigment Red 112, C.I. PigmentRed 122, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 16,C.I. Vat Blue 4, and C.I. Vat Blue 6;

(6) the ink jet ink composition of (5) wherein the pigment is present inan amount of from about 0.1 to about 30 wt % and is characterized by aparticle size of from about 0.1 to about 100 microns in diameter;

(7) the ink jet ink composition of (6) wherein the pigment is present inan amount of from about 2 to about 10 wt % and is characterized by aparticle size of from about 0.01 to about 10 microns in diameter;

(8) the ink jet ink composition of (7) wherein the pigment ischaracterized by a particle size from about 0.01 to about 5 microns indiameter;

(9) the ink jet ink composition of (3) wherein the dye is selected fromthe group of dyes consisting of basic, acid, and direct dyes;

(10) the ink jet ink compositions of (3) wherein the dye is a reactivedye;

(11) the ink jet ink composition of (3) wherein the dye is present in anamount of from about 0.1 to about 30 wt %;

(12) The ink jet ink composition of(l 1) wherein the dye is present inan amount of from about 2 to about 10 wt %;

(13) the ink jet ink composition of (3) wherein the metals and metaloxides are selected from the group consisting of silica, alumina,titania, and finely divided copper;

(14) the ink jet ink composition of (2) wherein the hybrid polymer ischaracterized by a first polymer having chemically attached thereto asecond polymer;

(15) the ink jet ink composition of (14) wherein the hybrid polymer ispresent in an amount to provide an amount from about 0.01% to about 30%,based on the weight of the polymer and wherein the polymer ischaracterized by an acid number from about 10 to about 300, a weightaverage molecular weight from about 500 to about 250,000, a softeningpoint from about 0 to about 150° C., and a glass transition temperaturefrom about -25 to 180° C.;

(16) the ink jet ink composition of (15) wherein the polymer ischaracterized by an acid number from about 20 to about 80, a weightaverage molecular weight from about 2,000 to about 35,000, a softeningpoint from about 40 to 90° C., and a glass transition temperature fromabout 25 to about 80° C.;

(17) the ink jet ink composition of (14) wherein the polymer is selectedfrom the group of naturally occurring polymers, synthetic analogues ofnaturally occurring polymers, synthetic polymers, and syntheticcopolymers;

(18) the ink jet ink composition of (17) wherein the naturally occurringpolymer is selected from the group of polymers consisting of alginicacid, carboxymethyl cellulose, and pectinic acid;

(19) the ink jet ink composition of (17) wherein the synthetic analoguesof naturally occurring polymers is selected from the group of polymersconsisting of rosin esters, lignosulfanates, nitrocellulose, andalcohol-soluble polysaccharides;

(20) the ink jet ink composition of (17) wherein the synthetic polymeris selected from the group of polymers consisting of polyacrylamide,polyacrylic acid, polyethylene oxide, polyethylene glycol,polymethacrylic acid, polyitaconic acid, polymaleic acid, polyvinylalcohol, and polyvinyl methyl ether;

(21) the ink jet ink composition of (17) wherein the synthetic copolymeris selected from the group of polymers consisting of styrene/acrylicacid, ethylene/vinyl acetate, acrylic acid/N-vinyl pyrrolidinone, andvinylnaphthalene/itaconate copolymers;

(22) the ink jet ink composition of (17) wherein the hybrid polymer isprepared by a polymerization method selected from the group consistingof solution polymerization, emulsion polymerization, suspensionpolymerization, and bulk polymerization;

(23) the ink jet ink composition of (2) further comprising a member ofthe group consisting of wax, polymer, antioxidant, biocide, corrosioninhibitor, and a combination thereof;

(24) the ink jet ink composition of claim 23 wherein the wax is selectedfrom the group consisting of petroleum wax, plant wax, animal wax,synthetic hydrocarbon wax higher fatty acid, higher alcohol, and aderivative thereof;

(25) the ink jet ink composition of (24) wherein the petroleum wax is amember of the group consisting of paraffin wax and micro crystallinewax;

(26) the ink jet ink composition of (24) wherein the plant wax is amember of the group consisting of candelilla wax and carnuba wax;

(27) the ink jet ink composition of (24) wherein the animal wax is amember of the group consisting of bees wax and lanolin;

(28) the ink jet ink composition of (24) wherein the synthetichydrocarbon wax is a member of the group consisting of a Fisher-Tropschwax and a polyethylene wax;

(29) the ink jet ink composition of (24) wherein the higher fatty acidis a member of the group consisting of stearic acid and lauric acid;

(30) the ink jet ink composition of (24) wherein the higher alcohol isselected from a member of the group consisting of stearyl alcohol and12-hydroxystearic acid;

(31) the ink jet ink composition of (23) wherein the polymer is a memberof the group consisting of alkyd resins, amides, acrylic polymers,benzoate esters, citrate plasticizers, cumarone-indene resins, dimerfatty acids, epoxy resins, fatty acids, ketone resins, maleateplasticizers, long chain alcohols, olefin resins, petroleum resins,phenolic resins, phthalate plasticizers, polyesters, polyvinyl alcoholresins, rosins, styrene resins, sulfones, sulfonamides, terpene resins,urethanes, vinyl resins, and derivatives and combinations thereof;

(32) the ink jet ink composition of (3 1) wherein the polymer ischaracterized by a melting point from about 40 to about 200° C. and asurface tension from about 20 to about 70 dynes/cm;

(33) the ink jet ink composition of (32) wherein the polymer ischaracterized by a melting point from about 60 to about 140° C. and asurface tension from about 30 to about 60 dynes/cm;

(34) the ink jet ink composition of (23) wherein the antioxidant ispresent in an amount from about 0.1% to about 1.0%, based on the weightof the ink composition;

(35) the ink jet ink composition of (23) wherein the biocide is presentin an amount from about 0.01% to about 5.0%, based on the weight of theink composition; and

(36) the ink jet ink composition of (23) wherein the corrosion inhibitoris present in an amount from about 0.1% to about 5.0%, based on theweight of the ink composition.

A further embodiment of the invention disclosed herein is:

(37) A method of printing comprising applying an ink jet ink compositioncomprising a colorant and a hybrid polymer on a substrate with arecording device;

(38) the method of (37) wherein the application of the ink compositionon the substrate is conducted by thermally melting the ink at atemperature above ambient temperature;

(39) the method of (38) wherein the application of the ink is selectedfrom the group consisting of hot melt ink jet and hot melt gravure;

(40) the method of (37) wherein the substrate is selected from the groupconsisting of porous substrates and nonporous substrates;

(41) the method of (40) wherein the porous substrate is selected fromthe group consisting of wood, paper, and textile;

(42) the method of (40) wherein the nonporous substrate is selected fromthe group consisting of glass, metal, and synthetic polymer film;

(43) the method of (42) wherein the metal is aluminum; and

(44) the method of (37) wherein the recording device is a piezo ink jetprinter.

Modifications to this invention will occur to those skilled in this art.Therefore, it is to be understood that this invention is not necessarilylimited to the particular embodiments disclosed; rather, it is intendedto cover all modifications which are within the true spirit and scope ofthis invention, as disclosed and claimed herein.

What is claimed is:
 1. A phase change ink jet ink composition comprisinga colorant and a hybrid polymer comprising a first polymer havingchemically attached thereto a second polymer, wherein the first polymerand second polymer are different polymers selected from the groupconsisting of naturally occurring polymers, synthetic analogues ofnaturally occurring polymers, synthetic polymers, and syntheticcopolymers.
 2. The ink jet ink composition of claim 1 wherein thecolorant is a member of the group of colorants selected from pigments,dyes, metals, metal oxides, and combinations thereof.
 3. The ink jet inkcomposition of claim 2 wherein the pigment is selected from the group oforganic and inorganic water-insoluble colorants and combinationsthereof.
 4. The ink jet ink composition of claim 3 wherein the pigmentis selected from the group of pigments consisting of C.I. Pigment Yellow1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 13, C.I. Pigment Red 5,C.I. Pigment Red 7, C.I. Pigment Red 12, C.I. Pigment Red 112, C.I.Pigment Red 122, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. PigmentBlue 16, C.I. Vat Blue 4, and C.I. Vat Blue
 6. 5. The ink jet inkcomposition of claim 4 wherein the pigment is present in an amount offrom about 0.1 to about 30 wt % and is characterized by a particle sizeof from about 0.1 to about 100 microns in diameter.
 6. The ink jet inkcomposition of claim 5 wherein the pigment is present in an amount offrom about 2 to about 10 wt % and is characterized by a particle size offrom about 0.01 to about 10 microns in diameter.
 7. The ink jet inkcomposition of claim 6 wherein the pigment is characterized by aparticle size from about 0.01 to about 5 microns in diameter.
 8. The inkjet ink composition of claim 2 wherein the dye is selected from thegroup of dyes consisting of basic, acid, and direct dyes.
 9. The ink jetink compositions of claim 2 wherein the dye is a reactive dye.
 10. Theink jet ink composition of claim 2 wherein the dye is present in anamount of from about 0.1 to about 30 wt %.
 11. The ink jet inkcomposition of claim 10 wherein the dye is present in an amount of fromabout 2 to about 10 wt %.
 12. The ink jet ink composition of claim 2wherein the metals and metal oxides are selected from the groupconsisting of silica, alumina, titania, and finely divided copper. 13.The ink jet ink composition of claim 1 wherein the hybrid polymer ispresent in an amount to provide an amount 0.01% to about 30%, based onthe weight of the polymer in gel form and wherein the polymer ischaracterized by an acid number from about 10 to about 300, a weightaverage molecular weight from about 500 to about 250,000, a softeningpoint from about 0 to about 150° C., and a glass transition temperaturefrom about -25 to 180° C.
 14. The ink jet ink composition of claim 13wherein the polymer is characterized by an acid number from about 20 toabout 80, a weight average molecular weight from about 2,000 to about35,000, a softening point from about 40 to 90° C., and a glasstransition temperature from about 25 to about 80° C.
 15. The ink jet inkcomposition of claim 1 wherein the naturally occurring polymer isselected from the group of polymers consisting of alginic acid,carboxymethyl cellulose, and pectinic acid.
 16. The ink jet inkcomposition of claim 1 wherein the synthetic analogues of naturallyoccurring polymers is selected from the group of polymers consisting ofrosin esters, lignosulfanates, nitrocellulose, and alcohol-solublepolysaccharides.
 17. The ink jet ink composition of claim 1 wherein thesynthetic polymer is selected from the group of polymers consisting ofpolyacrylamide, polyacrylic acid, polyethylene oxide, polyethyleneglycol, polymethacrylic acid, polyitaconic acid, polymaleic acid,polyvinyl alcohol, and polyvinyl methyl ether.
 18. The ink jet inkcomposition of claim 1 wherein the synthetic copolymer is selected fromthe group of polymers consisting of styrene/acrylic acid, ethylene/vinylacetate, acrylic acid/N-vinyl pyrrolidinone, andvinylnaphthalene/itaconate copolymers.
 19. The ink jet ink compositionof claim 1 wherein the hybrid polymer is prepared by a polymerizationmethod selected from the group consisting of solution polymerization,emulsion polymerization, suspension polymerization, and bulkpolymerization.
 20. The ink jet ink composition of claim 1 furthercomprising a member of the group consisting of wax, polymer,antioxidant, biocide, corrosion inhibitor, and a combination thereof.21. The ink jet ink composition of claim 20 wherein the wax is selectedfrom the group consisting of petroleum wax, plant wax, animal wax,synthetic hydrocarbon wax higher fatty acid, higher alcohol, and aderivative thereof.
 22. The ink jet ink composition of claim 21 whereinthe petroleum wax is a member of the group consisting of paraffin waxand micro crystalline wax.
 23. The ink jet ink composition of claim 21wherein the plant wax is a member of the group consisting of candelillawax and carnuba wax.
 24. The ink jet ink composition of claim 21 whereinthe animal wax is a member of the group consisting of bees wax andlanolin.
 25. The ink jet ink composition of claims wherein the synthetichydrocarbon wax is a member of the group consisting of a Fisher-Tropschwax and a polyethylene wax.
 26. The ink jet ink composition of claim 21wherein the higher fatty acid is a member of the group consisting ofstearic acid and lauric acid.
 27. The ink jet ink composition of claim21 wherein the higher alcohol is selected from a member of the groupconsisting of stearyl alcohol and 12-hydroxystearic acid.
 28. The inkjet ink composition of claim 20 wherein the polymer is a member of thegroup consisting of alkyd resins, amides, acrylic polymers, benzoateesters, citrate plasticizers, cumarone-indene resins, dimer fatty acids,epoxy resins, fatty acids, ketone resins, maleate plasticizers, longchain alcohols, olefin resins, petroleum resins, phenolic resins,phthalate plasticizers, polyesters, polyvinyl alcohol resins, rosins,styrene resins, sulfones, sulfonamides, terpene resins, urethanes, vinylresins, and derivatives and combinations thereof.
 29. The ink jet inkcomposition of claim 28 wherein the polymer is characterized by amelting point from about 40 to about 200° C. and a surface tension fromabout 20 to about 70 dynes/cm.
 30. The ink jet ink composition of claim29 wherein the polymer is characterized by a melting point from about 60to about 140° C. and a surface tension from about 30 to about 60dynes/cm.
 31. The ink jet ink composition of claim 20 wherein theantioxidant is present in an amount from about 0.1% to about 1.0%, basedon the weight of the ink composition.
 32. The ink jet ink composition ofclaim 20 wherein the biocide is present in an amount from about 0.01% toabout 5.0%, based on the weight of the ink composition.
 33. The ink jetink composition of claim 20 wherein the corrosion inhibitor is presentin an amount from about 0.1% to about 5.0%, based on the weight of theink composition.
 34. A method of printing comprising applying an ink jetink composition comprising a colorant and a hybrid polymer on asubstrate with a recording device wherein the hybrid polymer comprises afirst polymer having chemically attached thereto a second polymer,wherein the first polymer and second polymer are different polymersselected from the group consisting of naturally occurring polymers,synthetic analogues of naturally occurring polymers, synthetic polymers,and synthetic copolymers.
 35. The method of claim 34 wherein theapplication of the ink composition on the substrate is conducted bythermally melting the ink at a temperature above ambient temperature.36. The method of claim 35 wherein the application of the ink isselected from the group consisting of hot melt ink jet and hot meltgravure.
 37. The method of claim 34 wherein the substrate is selectedfrom the group consisting of porous substrates and nonporous substrates.38. The method of claim 37 wherein the porous substrate is selected fromthe group consisting of wood, paper, and textile.
 39. The method ofclaim 37 wherein the nonporous substrate is selected from the groupconsisting of glass, metal, and synthetic polymer film.
 40. The methodof claim 39 wherein the metal is aluminum.
 41. The method of claim 34wherein the recording device is a piezo ink jet printer.